(E)-5-(4-methoxyphenyl)pent-4-enoic acid

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (E)-5-(4-methoxyphenyl)pent-4-enoic acid
• 英文别名: (4E)-5-(4-methoxyphenyl)pent-4-enoic acid
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: MNKMFGIQBUBYHW-DUXPYHPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-5-(4-methoxyphenyl)pent-4-enoic acid 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (E)-5-(4-methoxyphenyl)pent-4-enyl methanesulfonate
  参考文献：
  名称：

  Enantioselective synthesis of 2-substituted and 3-substituted piperidines through a bromoaminocyclization process

  摘要：

  以氨基硫代氨基甲酸酯为催化剂，开发了一种烯烃酰胺的催化对映体选择性溴环化反应。通过银盐介导的重排反应，生成的对映体富集的 2-取代的 3-溴哌啶类化合物可以很容易地转化为 3-取代的哌啶类化合物。这一过程已被用于合成多巴胺能药物 Preclamol。

  DOI：

  10.1039/c2cc36578b
• 作为产物：
  描述：

  1'-羟基草蒿脑 在 正丁基锂 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 3.0h， 生成 (E)-5-(4-methoxyphenyl)pent-4-enoic acid
  参考文献：
  名称：

  Direct Catalytic Anti-Markovnikov Hydroetherification of Alkenols

  摘要：

  A direct intramolecular anti-Markovnikov hydroetherification reaction of alkenols is described. By employing Catalytic quantities of commercially available 9-mesityl-10-methylacridinium perchlorate and 2-phenyl-malononitrile as a redox-cycling source of a H-atom, we report the anti-Markovnikov hydroetherification of alkenes with complete regioselectivity, In addition, we present results demonstrating that this novel catalytic system can be applied to the anti-Markovnikov hydrolactonization of alkenoic acids.

  DOI：

  10.1021/ja309635w

文献信息

• Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones
  作者：Robert J Perkins、Hai-Chao Xu、John M Campbell、Kevin D Moeller

  DOI：10.3762/bjoc.9.186

  日期：——

  Carboxylic acids have been electro-oxidatively coupled to electron-rich olefins to form lactones. Kolbe decarboxylation does not appear to be a significant competing pathway. Experimental results indicate that oxidation occurs at the olefin and that the reaction proceeds through a radical cation intermediate.

  羧酸已与富电子烯烃电氧化偶联以形成内酯。Kolbe 脱羧似乎不是一个重要的竞争途径。实验结果表明氧化发生在烯烃处，反应通过自由基阳离子中间体进行。
• Preparation of α-Acyloxy Ketones via Visible-Light-Driven Aerobic Oxo-Acyloxylation of Olefins with Carboxylic Acids
  作者：Qing-Bao Zhang、Yong-Liang Ban、Da-Gang Zhou、Pan-Pan Zhou、Li-Zhu Wu、Qiang Liu

  DOI：10.1021/acs.orglett.6b02560

  日期：2016.10.21

  developed a visible-light driven oxo-acyloxylation of aryl alkenes with carboxylic acids and molecular oxygen. A metal-free photoredox system, consisting of an acridinium photocatalyst, an organic base, and molecular sieve (MS) 4 Å, promotes chemoselective aerobic photooxidation of aryl alkenes. This approach may provide a green, practical, and metal-free protocol for a wide range of α-acyloxy ketones.

  我们开发了可见光驱动的芳基烯烃与羧酸和分子氧的羰基酰氧基化反应。由metal啶光催化剂，有机碱和4Å分子筛组成的无金属氧化还原体系可促进芳基烯烃的化学选择性好氧光氧化。这种方法可以为多种α-酰氧基酮提供绿色，实用且不含金属的方案。
• Stereospecific Alkene Aziridination Using a Bifunctional Amino-Reagent: An Aza-Prilezhaev Reaction
  作者：Joshua J. Farndon、Tom A. Young、John F. Bower

  DOI：10.1021/jacs.8b10485

  日期：2018.12.26

  deprotection (TFA) of O-Ts activated N-Boc hydroxylamines triggers intramolecular aziridination of N-tethered alkenes to provide complex N-heterocyclic ring systems. Synthetic and computational studies corroborate a diastereospecific aza-Prilezhaev-type mechanism. The feasibility of related intermolecular alkene aziridinations is also demonstrated.

  O-Ts 活化的 N-Boc 羟胺的原位脱保护 (TFA) 触发了 N-系链烯烃的分子内氮丙啶化，以提供复杂的 N-杂环系统。合成和计算研究证实了一种非对映特异性 aza-Prilezhaev 型机制。还证明了相关分子间烯烃氮丙啶的可行性。
• Orthogonally Protected 1,2-Diols from Electron-Rich Alkenes Using Metal-Free Olefin <i>syn</i>-Dihydroxylation
  作者：Ignacio Colomer、Rosimeire Coura Barcelos、Kirsten E. Christensen、Timothy J. Donohoe

  DOI：10.1021/acs.orglett.6b02959

  日期：2016.11.18

  A new method for the stereoselective metal-free syn-dihydroxylation of electron-rich olefins is reported, involving reaction with TEMPO/IBX in trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) and the addition of a suitable nucleophile. Orthogonally protected syn 1,2-diols were obtained with high levels of diastereocontrol, and these products were selectively deprotected and selectively functionalized

  报道了一种用于富电子烯烃的立体选择性无金属顺式二羟基化的新方法，该方法涉及在三氟乙醇（TFE）或六氟异丙醇（HFIP）中与TEMPO / IBX反应并添加合适的亲核试剂。获得具有高水平非对映异构控制的被正交保护的顺式1,2-二醇，并且将这些产物选择性地脱保护并选择性地官能化为合成上有用的化合物。
• HFIP Solvent Enables Alcohols To Act as Alkylating Agents in Stereoselective Heterocyclization
  作者：Yuxiang Zhu、Ignacio Colomer、Amber L. Thompson、Timothy J. Donohoe

  DOI：10.1021/jacs.9b02198

  日期：2019.4.24

  method for the stereoselective synthesis of highly functionalized oxygen heterocycles using allyl or benzyl alcohols as alkylating agents is presented. The process is efficient and atom economic, generating water as the only stoichiometric byproduct. Substoichiometric amounts of Ti(OiPr)4 in HFIP solvent are key to this reactivity, and the method tolerates a broad substitution pattern on both the alcohol

  提出了一种使用烯丙醇或苯甲醇作为烷化剂立体选择性合成高度官能化氧杂环的新方法。该过程高效且原子经济，产生的水是唯一的化学计量副产品。HFIP 溶剂中低于化学计量的 Ti(OiPr)4 是这种反应性的关键，并且该方法在醇引发剂和高烯丙醇底物上都可以容忍广泛的取代模式。初步的机理研究揭示了钛配合物与 HFIP 的原位形成，这可能会引发环化反应。产品的进一步立体选择性功能化允许获得各种有趣的杂环结构。